US5180841A - Preparation of 1-amino-2-chloro-4-hydroxyanthraquinone - Google Patents

Preparation of 1-amino-2-chloro-4-hydroxyanthraquinone Download PDF

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US5180841A
US5180841A US07/823,814 US82381492A US5180841A US 5180841 A US5180841 A US 5180841A US 82381492 A US82381492 A US 82381492A US 5180841 A US5180841 A US 5180841A
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amino
hydroxyanthraquinone
sulfuric acid
chloro
preparation
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US07/823,814
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Gerhard Epple
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
    • C09B1/503—Amino-hydroxy-anthraquinones; Ethers and esters thereof unsubstituted amino-hydroxy anthraquinone
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
    • C07C225/26—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings
    • C07C225/32—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings of condensed quinone ring systems formed by at least three rings
    • C07C225/34—Amino anthraquinones
    • C07C225/36—Amino anthraquinones the carbon skeleton being further substituted by singly-bound oxygen atoms

Definitions

  • the present invention relates to a novel for preparing 1-amino-2-chloro-4-hydroxyanthraquinone I by chlorinating 1-amino-4-hydroxy-2,3-dihydroanthraquinone II. ##STR1##
  • 1-amino-2-chloro-4-hydroxyanthraquinone can be prepared by chlorinating 1-amino-4-hydroxyanthraquinone III ##STR2## in 90-100% aqueous sulfuric acid or in up to 2% oleum.
  • the process of the present invention is carried out by dissolving the starting material II in from 4 to 20 times, preferably from 6 to 10 times, the amount of 92-100%, preferably 96-99%, sulfuric acid with stirring and introducing chlorine at from 20° to 80° C., preferably at from 40° to 70° C., at least 2 mol of chlorine being necessary.
  • the course of the reaction is advantageously monitored by thin layer chromatography.
  • the oxidation of II to III and the chlorination of III take place simultaneously.
  • the reaction is interrupted when all of II and more than 97 % of III have been converted, either by pouring the reaction mixture into water or slowly adding water to the reaction mixture to precipitate the product.
  • 1-Amino-2-chloro-4-hydroxyanthraquinone is an important intermediate in the preparation of red anthraquinone dyes, for example in the preparation of Disperse Red 60, C.I. 60756.
  • Example 2 80 g of 95.6% pure 1-amino-4-hydroxy-2,3-dihydroanthraquinone are dissolved in 506 g of 97.5% sulfuric acid and chlorinated as indicated in Example 2. The product is precipitated by the dropwise addition of 210 g of water and worked up as in Example 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The useful dye intermediate 1-amino-2-chloro-4-hydroxyanthraquinone is prepared by chlorinating 1-amino-4-hydroxy-2,3-dihydroanthraquinone with chlorine in concentrated sulfuric acid.

Description

The present invention relates to a novel for preparing 1-amino-2-chloro-4-hydroxyanthraquinone I by chlorinating 1-amino-4-hydroxy-2,3-dihydroanthraquinone II. ##STR1##
It is known from DE-A-38 32 740 that 1-amino-2-chloro-4-hydroxyanthraquinone can be prepared by chlorinating 1-amino-4-hydroxyanthraquinone III ##STR2## in 90-100% aqueous sulfuric acid or in up to 2% oleum.
However, starting from 1,4-dihydroxyanthraquinone IV (quinizarine), the preparation of sufficiently pure III requires at least two synthesis stages, namely the conversion to 1,4-diamino-2,3-dihydroanthraquinone V (leukamine) in ammonia and subsequent conversion to III in sulfuric acid with manganese dioxide. The manganese dioxide makes it difficult to regenerate the sulfuric acid. ##STR3##
The preparation of II is known from French Patent 602,882 or British Patent 507,065.
In general, the process of the present invention is carried out by dissolving the starting material II in from 4 to 20 times, preferably from 6 to 10 times, the amount of 92-100%, preferably 96-99%, sulfuric acid with stirring and introducing chlorine at from 20° to 80° C., preferably at from 40° to 70° C., at least 2 mol of chlorine being necessary.
The course of the reaction is advantageously monitored by thin layer chromatography. The oxidation of II to III and the chlorination of III take place simultaneously. The reaction is interrupted when all of II and more than 97 % of III have been converted, either by pouring the reaction mixture into water or slowly adding water to the reaction mixture to precipitate the product.
1-Amino-2-chloro-4-hydroxyanthraquinone is an important intermediate in the preparation of red anthraquinone dyes, for example in the preparation of Disperse Red 60, C.I. 60756.
The process of the present invention will now be more particularly described by way of example.
EXAMPLE 1
500 g of 95% pure 1-amino-4-hydroxy-2,3-dihydroanthraquinone (II) are introduced into 3000 g of 97.5% sulfuric acid with stirring. The mixture is heated to 60° C. and 308 g of chlorine are passed in over 24 hours. Then nitrogen is passed through the reaction mixture for 2 hours to drive out dissolved hydrogen chloride.
Then 1220 g of water are added dropwise at 60° C. in the course of 3 hours, and the product precipitates. It is filtered off with suction, washed with 1500 g of 60% sulfuric acid and then washed neutral with water and dried.
Yield: 509.8 g of 92.3 % pure product, i.e. 87.3% of theory.
EXAMPLE 2
440 g of 90.9% pure 1-amino-4-hydroxy-2,3-dihydroanthraquinone (II) are dissolved in 2400 g of 97.4% sulfuric acid. Chlorine is introduced at 60° C. until only traces of 1-amino-4-hydroxyanthraquinone III are detectable by thin layer chromatography. Nitrogen is passed through for 2 hours, and then 960 g of water are added dropwise at 60°-90° C. over 2 hours. The reaction mixture is cooled down and the precipitated product is filtered off with suction. It is washed with 2000 g of 60% sulfuric acid, and then with water and dried.
Yield: 456.6 g of 90.9% pure product; i.e. 91.4% of theory.
EXAMPLE 3
80 g of 95.6% pure 1-amino-4-hydroxy-2,3-dihydroanthraquinone are dissolved in 506 g of 97.5% sulfuric acid and chlorinated as indicated in Example 2. The product is precipitated by the dropwise addition of 210 g of water and worked up as in Example 2.
Yield: 85.6 g of 96.5% pure product, i.e. 91% of theory.
EXAMPLE 4
1072 g of 93.3% pure 1-amino-4-hydroxy-2,3-dihydroanthraquinone are introduced into 6000 g of 97.5% sulfuric acid and heated to 60° C. 700 g of chlorine are introduced at 60°-65° C. in the course of 18 hours. Then nitrogen is passed through the reaction mixture in order to drive out dissolved hydrogen chloride.
Then 2400 g of water are added at 90°-95° C., which precipitates the product, which after cooling down to 20°-25° C. is filtered off and washed with sulfuric acid and water.
Drying leaves 1033 g of 92% pure 1-amino-2-chloro-4-hydroxyanthraquinone.

Claims (3)

We claim:
1. A process for preparing 1-amino2-chloro-4-hydroxyanthraquinone, which comprises chlorinating 1-amino-4-hydroxy-2,3-dihydroanthraquinone with at least 2 mol of chlorine in concentrated sulfuric acid.
2. A process as claimed in claim 1, wherein from 4 to 20 times the amount of 92-100% sulfuric acid is used, based on the dihydroanthraquinone.
3. A process as claimed in claim 1, wherein the chlorination is carried out at from 40° to 70° C.
US07/823,814 1991-01-23 1992-01-22 Preparation of 1-amino-2-chloro-4-hydroxyanthraquinone Expired - Lifetime US5180841A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4101875A DE4101875A1 (en) 1991-01-23 1991-01-23 METHOD FOR PRODUCING 1-AMINO-2-CHLORINE-4-HYDROXI ANTHRACHINONE
DE4101875 1991-01-23

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US5180841A true US5180841A (en) 1993-01-19

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US (1) US5180841A (en)
EP (1) EP0496113B1 (en)
JP (1) JP2956806B2 (en)
DE (2) DE4101875A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR602882A (en) * 1924-09-11 1926-04-02 Improvements in the manufacture of basic derivatives of the aromatic series, and resulting products
GB507065A (en) * 1937-12-07 1939-06-07 Henry Charles Olpin Manufacture of compounds of the anthraquinone series
DE2428337A1 (en) * 1974-06-12 1975-12-18 Basf Ag 1-Amino-2-halo-4-hydroxy-anthraquinones prepn - by hydroxylation of alcohol-wet filter cakes of corresponding 2,4-dihalo -cpds
EP0361253A2 (en) * 1988-09-27 1990-04-04 BASF Aktiengesellschaft Process for the preparation of 1-amino-2-chloro-4-hydroxy-anthraquinone

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR602882A (en) * 1924-09-11 1926-04-02 Improvements in the manufacture of basic derivatives of the aromatic series, and resulting products
GB507065A (en) * 1937-12-07 1939-06-07 Henry Charles Olpin Manufacture of compounds of the anthraquinone series
DE2428337A1 (en) * 1974-06-12 1975-12-18 Basf Ag 1-Amino-2-halo-4-hydroxy-anthraquinones prepn - by hydroxylation of alcohol-wet filter cakes of corresponding 2,4-dihalo -cpds
EP0361253A2 (en) * 1988-09-27 1990-04-04 BASF Aktiengesellschaft Process for the preparation of 1-amino-2-chloro-4-hydroxy-anthraquinone
DE3832740A1 (en) * 1988-09-27 1990-04-05 Basf Ag METHOD FOR PRODUCING 1-AMINO-2-CHLORINE-4-HYDROXY-ANTHRACHINONE
US4997960A (en) * 1988-09-27 1991-03-05 Basf Aktiengesellschaft Preparation of 1-amino-2-chloro-4-hydroxyanthraquinone

Also Published As

Publication number Publication date
DE59106947D1 (en) 1996-01-04
EP0496113B1 (en) 1995-11-22
JPH04312560A (en) 1992-11-04
EP0496113A1 (en) 1992-07-29
JP2956806B2 (en) 1999-10-04
DE4101875A1 (en) 1992-07-30

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